以固態反應法在氧化鋁單晶表面生長鎂鋁尖晶石磊晶薄膜

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研究生：	陳俊任 Chun-Jen Chen
論文名稱：	以固態反應法在氧化鋁單晶表面生長鎂鋁尖晶石磊晶薄膜 The growth of an epitaxial Mg-Al spinel layer on sapphire by solid-state reactions
指導教授：	陳志臣 Jyh-Chen Chen
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 機械工程學系 Department of Mechanical Engineering
畢業學年度：	93
語文別：	中文
論文頁數：	54
中文關鍵詞：	磊晶薄膜、固態反應法、氧化鋁、鎂鋁尖晶石
外文關鍵詞：	Mg-Al spinel, epitaxy, sapphire, solid-state reaction
相關次數：	點閱：16 下載：0
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本研究主要是以固態反應法在藍寶石表面生長鎂鋁尖晶石薄膜，利用
物理汽相沈積（PVD）及熱處理製程，生長出具優先取向性之磊晶薄膜，
並透過後續檢測等技術，確定其薄膜的成分與結構等性質。同時，藉由熱
處理的製程參數之控制，逐步探討參數條件如何影響表面薄膜的成分與性
質改變。
在實驗結果可以發現，反應薄膜在不同的熱處理溫度下，會有不同的
反應速率，並隨著溫度的升高而增加；並且在氧化鎂未反應完全之前，尖
晶石生成物之反應層厚度也會隨著熱處理時間的增加而增加，呈現線性的
變化趨勢。此外，在薄膜的磊晶方向上，由XRD 實驗得知在不同軸向的
氧化鋁基板，會形成不同方向性的尖晶石磊晶層，並發現（hhh）方向之
Mg-Al spinel 容易生長在C軸及A軸氧化鋁上，而（hh0）方向之Mg-Al spinel
則易生長在M 軸氧化鋁基板上。同時透過平面上方向的量測與表面結構的
觀察，可以獲得spine 磊晶層與sapphire 基板間in-plane 方向上的關係。另
外也可以確定的是spinel（hhh）生長的結構面為三方對稱形紋路，且表面
的對稱結構之方位與原子排列結構的方向有關。透過此篇論文在氧化鋁基
板上生成鎂鋁尖晶石所做的各項性質探討，可以作為生長其他spinel 結構
之磊晶薄膜的參考依據。

In this study, an epitaxial Mg-Al spinel layer was successfully grown on a
sapphire single crystal surface using solid-state reactions. The processes of
solid-state reactions with PVD and heat treatment were applied to grow
epitaxial layer with preferred orientation. And the layer composition and
structure can be confirmed by the further analyses. Through the controlling of
the heat treatment parameters, the variation of compositions and properties
influenced by different conditions on surface layer had been discussed.
From the experiment results, reaction layer showed different reaction rate
with various heat treatment, and it was proportion to the temperature and
duration. In additional, the orientation of epitaxial Mg-Al spinel layer would
depend on the cut of sapphire substrate. The hhh-type orientated spinel layer
preferred to grow on C- and A-plane sapphire, and the hh0-type orientated
spinel layer preferred to grow on M-plane sapphire. Simultaneously, the
in-plane orientation relationship between spinel epitaxial layer and sapphire
substrate could be obtained by φ scan. The morphology of the epitaxial spinel
layer surface will present a particular three-fold symmetrical structure by scanning
electron microscope. The model of atomic arrangement was employed to explain
the relationship between the surface morphology of spinel and its miller index.

目錄
摘要..........................................................I
英文摘要..................................................... II
目錄.........................................................III
圖表目錄..................................................... V
符號說明....................................................VII
第一章、緒論...................................................1
1.1 前言...................................................1
1.2 晶體性質與應用.........................................2
1.3 尖晶石相關研究. ........................................3
1.3.1 生長Mg-Al spinel 的反應機制.........................3
1.3.2 Mg-Al spinel 的優先取向性...........................6
1.3.3 spinel 表面結構特性................................8
1.4 研究動機和目的.........................................9
第二章、實驗方法與檢測........................................10
2.1 實驗設備..............................................10
2.1.1 射頻式磁控濺鍍...................................10
2.1.2 高溫熱處理爐.................................... 11
2.2 實驗流程..............................................11
2.2.1 鍍膜條件.........................................11
2.2.2 熱處理條件.......................................12
2.3 性質檢測與分析........................................13
2.3.1 成分分析.........................................13
2.3.2 方向性分析.......................................13
2.3.3 微結構分析.......................................14
IV
第三章、實驗結果與討論........................................16
3.1 表面成分分析..........................................16
3.2 薄膜擴散分析..........................................18
3.3 薄膜優先取向之分析....................................22
3.3.1 薄膜之垂直取向...................................22
3.3.2 薄膜與基板間之in-plane orientation 關係..............22
3.4 表面微結構分析........................................26
第四章、結論..................................................29
參考文獻..................................................... 31
V
圖表目錄
表1.1、鎂鋁尖晶石與氧化鋁之材料特性比較........................37
表3.1、面心立方體之結晶面、表面原子密度及鄰近原子數.............37
圖1.1、氧化鎂（MgO）與氧化鋁（Al2O3）之二元相圖...................38
圖1.2、Inert marker 實驗於sapphire 試片上之SEM 破斷面圖..........39
圖1.3、MgO 與Al2O3 之擴散機制示意圖...........................39
圖1.4、MgO/sapphire 反應前後之介面變化示意圖................... 40
（a）反應前，MgO/sapphire 介面呈現不連慣性
（b）反應後，MgAl2O4/sapphire 介面呈現連貫性
圖1.5、TEM 觀察MgO/sapphire 反應前後之介面之變化.............. 41
圖1.6、Ni-Al spinel 生長於{11
−2
0} Al2O3 塊材基板表面的SEM 圖.....41
圖2.1、金屬鎂（Mg）薄膜破斷面之SEM 圖........................42
圖2.2、In-plane orientation 之量測示意圖
（a）HRXRD 機台俯視圖（b）試片載具側視圖..............42
圖3.1、濺鍍Mg 金屬薄膜於
（a）A軸sapphire（b）C軸sapphire 上的XRPD檢測圖..........43
圖3.2、熱處理溫度1300℃，停留5-20 小時
（a）A 軸sapphire（b）C 軸sapphire 的XRPD 檢測..........44
圖3.3、熱處理溫度1600℃，停留5-30 小時
（a）A 軸sapphire（b）C 軸sapphire 的XRPD 檢測圖..........45
圖3.4、C 軸sapphire 濺鍍鎂薄膜後，經過
（a）1300℃ 5 小時（b）1600℃ 5 小時 之固態反應的試片表面..46
圖3.5、試片表面氧化鎂（MgO）粉末的XRPD 檢測圖
（上圖為實驗結果，下圖為標準繞射峰）...................47
VI
圖3.6、EPMA 之Line profile 掃瞄圖
（C 軸sapphire 經1600℃ 35 小時熱處理）.................48
圖3.7、鎂的分佈厚度與固態反應時間的關係圖.....................48
圖3.8、spinel 薄膜破斷面之SEM 圖
（A 軸sapphire 經1600℃ 30 小時熱處理）.................49
圖3.9、spinel 薄膜破斷面之EDS-Mapping 圖
（同圖3.7 之試片，觀察位置與圖3.8 相同）................49
圖3.10、C 軸sapphire 試片之spinel（110）、（100）與
sapphire R 軸（10
−1
2）的XRD φ scan........................50
圖3.11、A 軸sapphire 試片之（100）spinel 與
M軸（10
−1
0）sapphire 的XRD φ scan......................50
圖3.12、sapphire 晶格結構（a）俯視圖（b）側視圖..................51
圖3.13、固態反應生長spinel 於M 軸sapphire 試片的XRPD 檢測......51
圖3.14、C 軸sapphire 經1600℃ 30 小時熱處理後之SEM 圖..........52
圖3.15、A軸sapphire 經1600℃ 30 小時熱處理後之SEM圖.......... .52
圖3.16、MgAl2O4 在（111）的原子排列結構圖......................53
圖3.17、C 軸sapphire 經1600℃ 30 小時熱處理後之勞厄繞射圖
（同圖3.14 之試片）.....................................53
圖3.18、A 軸sapphire 經1600℃ 30 小時熱處理後之勞厄繞射圖
（同圖3.15 之試片）.....................................54

                                

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